CN103170346B - A kind of Fe of tungsten oxide finishing 2o 3catalyst, preparation method and its usage - Google Patents

A kind of Fe of tungsten oxide finishing 2o 3catalyst, preparation method and its usage Download PDF

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CN103170346B
CN103170346B CN201310123813.5A CN201310123813A CN103170346B CN 103170346 B CN103170346 B CN 103170346B CN 201310123813 A CN201310123813 A CN 201310123813A CN 103170346 B CN103170346 B CN 103170346B
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贺泓
刘福东
连志华
谢利娟
石晓燕
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The present invention relates to a kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3(x=2 ~ 3), described WO xthe mass percent accounting for described catalyst is 1 ~ 10wt.%.The invention also discloses the preparation method of above-mentioned catalyst.The Fe of surface unmodified 2o 3material NH 3selective Catalytic Reduction of NO x(NH 3-SCR) activity is extremely low, and operating temperature window is extremely narrow, and has a large amount of N 2o accessory substance generates, and passes through WO xafter finishing, NH 3-SCR catalytic activity and N 2generate selective all have very significantly improve, be suitable for very much stationary source and moving source NO xcatalytic removal.

Description

A kind of Fe of tungsten oxide finishing 2o 3catalyst, preparation method and its usage
Technical field
The present invention relates to a kind of Fe of tungsten oxide finishing 2o 3catalyst, preparation method and its usage, described catalyst is used for NH 3selective Catalytic Reduction of NO x.
Background technology
Ferriferous oxide may be used for multiple catalytic reaction as eco-friendly catalysis material.Due to F e 3+and F e 2+between there is good redox cycle ability, Fe is catalyst based also has good catalyzing N H 3selective reduction NO xability (NH 3-SCR), can be used for stationary source and moving source NO xcatalytic removal, to replace traditional vanadium base (V 2o 5-WO 3(MoO 3)/TiO 2) catalyst system.
Researchers mainly pay close attention to Fe early stage 2o 3morphology controllable synthesis (X.Mou, B.Zhang, Y.Li, L.Yao, X.Wei, D.S.Su, W.Shen, Angew.Chem.Int.Ed., 2012,51:2989), the Fe of material 2o 3material high-dispersion load (N.Apostolescu, B.Geiger, K.Hizbullah on a support material, M.T.Jan, S.Kureti, D.Reichert, F.Schott, W.Weisweiler, Appl.Catal.B:Environ., 2006,62:104) and containing synthesis (F.Liu, the H.He of Fe composite oxides, C.Zhang, Chem.Commun., 2008,2043) etc.The earlier application of CN101380578A, the applicant but the earlier application of undocumented patent CN201310007168.0, the applicant but undocumented patent CN201310034144.4 all relate to and prepare ferrotitanium composite oxides thing, ferrotungsten titanium composite oxide, iron cerium-titanium composite oxide material effectively to improve the catalyst based denitration performance of Fe and anti-H 2o/SO 2the method of poisoning capability.
Tungsten oxide (WO 3) effectively can improve NH as a kind of conventional catalyst promoter 3the heat endurance of-SCR catalyst, surface acidity and SCR activity (W.Shan, F.Liu, H.He, X.Shi, C.Zhang, Chem.Commun., 2011,47,8046; PCT/CN2011/081962; CN102302930A; CN102000560A; L.Chen, J.Li, W.Ablikim, J.Wang, H.Chang, L.Ma, J.Xu, M.Ge, H. Arandiyan, Catal.Lett., 2011,141,1859), be employed successfully in CeO 2the finishing of material is to improve denitration performance (Z.Ma, D.Weng, X.Wu, Z.Si, J.Environ.Sci., 2012,24,1305).
But, in prior art, seldom some researchers have reported that Fe 2o 3material carries out finishing significantly to improve its NH 3-SCR reactivity worth.
Summary of the invention
An object of the present invention is the Fe providing a kind of tungsten oxide finishing 2o 3catalyst, tungsten oxide finishing effectively can regulate Fe 2o 3the surface acidity of material and redox ability, thus significantly improve its NH in middle high temperature section 3-SCR reactivity.
In order to achieve the above object, present invention employs following technical scheme:
A kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 1 ~ 10wt.%.
Preferably, described WO xthe mass percent accounting for described catalyst is 1.5 ~ 8.5wt.%, preferably 3 ~ 6wt.%, further preferred 5wt.%.WO xthe NH when mass percent accounting for described catalyst is 1 ~ 10wt.% 3-SCR activity can significantly improve, but WO xduring too high levels, activity can decline, and when increasing tungsten oxide, cost can improve, and optimum is 5wt.%.
Described WO xthe mass percent accounting for described catalyst is such as 1.8wt.%, 2.5wt.%, 3.5wt.%, 4wt.%, 4.5wt.%, 5wt.%, 5.5wt.%, 6wt.%, 6.5wt.%, 7wt.%, 7.5wt.%, 8wt.%, 9wt.%, 9.5wt.%.
Two of object of the present invention is the Fe providing a kind of tungsten oxide finishing as above 2o 3the preparation method of catalyst, the catalyst adopting sluggish precipitation of the present invention and infusion process to obtain is at the NH of middle high temperature section 3-SCR reactivity is high, has very excellent anti-SO 2poisoning performance, high high-temp stability is excellent, and operating temperature window is wide.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1) prepare source of iron solution, add excess urea precipitating reagent in solution, make precipitation of iron ions complete, by the precipitated product suction filtration obtained, washing, dry, roasting, obtains Fe 2o 3;
(2) under oxalic acid existence condition, preparation tungsten source solution, adds Fe in the solution of tungsten source 2o 3powder, after stirring through rotary evaporation by solution evaporate to dryness, dry, roasting, obtains the Fe of tungsten oxide finishing 2o 3catalyst.
Described source of iron is selected from the mixture of any one or at least two kinds in ferric nitrate, ferric sulfate, ferric phosphate or iron chloride, preferred ferric nitrate.The mixture of described source of iron such as iron chloride and ferric phosphate, the mixture of ferric phosphate and ferric sulfate, the mixture of ferric sulfate and ferric nitrate, the mixture of iron chloride and ferric sulfate, the mixture of ferric phosphate and ferric nitrate, the mixture of iron chloride, ferric phosphate and ferric sulfate, the mixture of iron chloride, ferric phosphate, ferric sulfate and ferric nitrate.
In sluggish precipitation, make precipitating reagent with urea, precipitation source of iron, urea and the amount of substance of source of iron are than for can precipitating completely during 1.5:1 in theory, because urea likely exists the problem of not exclusively hydrolysis, therefore need to add excess urea.Urea is hydrolyzed, it is the process of a slow releasing hydroxide ion and carbanion, the slow hydrolysis of urea makes the reactant concentration in solution around iron ion that too large change can not occur, relative to other precipitating reagents as ammoniacal liquor and carbonic hydroammonium etc., precipitate with being more conducive to oxide precursor uniform particles.
Urea/source of iron mol ratio is 8 ~ 12:1, such as 8.2:1,8.4:1,8.6:1,8.8:1,9:1,9.2:1,9.4:1,9.6:1,9.8:1,10.2:1,10.6:1,10.8:1,11:1,11.4:1,11.8:1, preferred 10:1.
Urea/source of iron mol ratio is larger, hydrolysis of urea and the ammonia amount that discharges is corresponding increases, and solution alkaline strengthens, and sedimentary growing amount also increases thereupon, and precipitation is more complete, and productive rate also increases gradually.Meanwhile, the degree of supersaturation of precipitation increases, theoretical according to Chemical Kinetics, and degree of supersaturation increases, and the generating rate of crystal grain is faster, makes nucleation rate apparently higher than the speed of growth of nucleus, is conducive to generating small size particle.When urea/source of iron mol ratio is excessive, sedimentary recruitment is not remarkable, and precipitation is close to completely, and excessive concentration, waste raw material, increase cost.
Described precipitation temperature is 80 ~ 100 DEG C, such as 81 DEG C, 83 DEG C, 85 DEG C, 87 DEG C, 89 DEG C, 91 DEG C, 91.5 DEG C, 92 DEG C, 92.5 DEG C, 93 DEG C, 93.5 DEG C, 94 DEG C, 94.5 DEG C, 95 DEG C, 95.5 DEG C, 96 DEG C, 96.5 DEG C, 97 DEG C, 97.5 DEG C, 98 DEG C, 98.5 DEG C, 99 DEG C, 99.5 DEG C, preferably 90 DEG C.
The time of described precipitation is 8 ~ 15h, such as 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, preferably 9 ~ 13h, further preferred 12h.
The temperature of step (1) described drying is 90 ~ 110 DEG C, such as 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C, 95 DEG C, 96 DEG C, 97 DEG C, 98 DEG C, 99 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C, preferably 95 ~ 105 DEG C, preferably 100 DEG C further.
The time of step (1) described drying is 3 ~ 8h, such as 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, preferably 3.5 ~ 6.5h, further preferred 5h.
Step (1) described roasting is carried out in air atmosphere, and described sintering temperature is 400 ~ 600 DEG C, such as 430 DEG C, 460 DEG C, 510 DEG C, 540 DEG C, 570 DEG C, 580 DEG C, 590 DEG C, preferably 500 ~ 600 DEG C, preferably 500 DEG C further.
Step (1) described roasting time is 2 ~ 5h, such as 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferred 3h.
Preparation tungsten source solution, and take Fe 2o 3powder infusion in solution, control WO xthe mass percent accounting for described catalyst is 1 ~ 10wt.%.
Described tungsten source is selected from tungstates or/and tungsten phosphate, preferred ammonium tungstate or/and sodium tungstate, further preferably ammonium tungstate.
The time of step (2) described stirring is 0.5 ~ 1.5 hour, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, preferably 1 hour.
The temperature of described rotary evaporation evaporate to dryness is 70 ~ 90 DEG C, such as 72 DEG C, 74 DEG C, 76 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C, preferably 73 ~ 87 DEG C, preferably 80 DEG C further.
The temperature of step (2) described drying is 90 ~ 110 DEG C, such as 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C, 95 DEG C, 96 DEG C, 97 DEG C, 98 DEG C, 99 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C, 106 DEG C, 107 DEG C, 108 DEG C, 109 DEG C, preferably 95 ~ 105 DEG C, preferably 100 DEG C further.
The time of step (2) described drying is 3 ~ 8h, such as 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, preferably 3.5 ~ 6.5h, further preferred 5h.
Step (2) described roasting is carried out in air atmosphere, and described sintering temperature is 400 ~ 600 DEG C, such as 430 DEG C, 460 DEG C, 510 DEG C, 540 DEG C, 570 DEG C, 580 DEG C, 590 DEG C, preferably 500 ~ 600 DEG C, preferably 500 DEG C further.
Step (2) described roasting time is 2 ~ 5h, such as 2.4h, 2.7h, 3.1h, 3.4h, 3.6h, 3.9h, 4.2h, 4.5h, 4.8h, preferred 3h.
Preferably sieve step (2) product of roasting compressing tablet 20 ~ 80 orders, preferably 40 ~ 60 orders.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1 ') preparation iron nitrate solution, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 10:1,12h is stirred continuously under 90 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 100 DEG C of oven drying 5h afterwards, last in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, obtain Fe 2o 3;
(2 '), preparation ammonium tungstate solution, added Fe in ammonium tungstate solution under oxalic acid existence condition 2o 3powder, stirs after 1h, through rotary evaporation at 80 DEG C by solution evaporate to dryness, 100 DEG C of dry 5h, finally in air atmosphere in 500 DEG C of roasting 3h, compressing tablet sieves into 40 ~ 60 orders, obtains the Fe of tungsten oxide finishing 2o 3catalyst.
Three of object of the present invention is the Fe providing a kind of tungsten oxide finishing as above 2o 3the purposes of catalyst, described catalyst is used for NH 3selective Catalytic Reduction of NO x.
Compared with prior art, the present invention has following beneficial effect:
(1) Fe of surperficial unmodified 2o 3material NH 3-SCR catalytic activity is extremely low, and operating temperature window is extremely narrow, and has a large amount of N 2o accessory substance generates, and passes through WO xafter finishing, NH 3-SCR catalytic activity and N 2generate selective all have very significantly improve;
(2) the present invention adopts the simple precipitation method and infusion process to synthesize tungsten oxide WO first xthe Fe of finishing 2o 3catalyst, preferred WO xload capacity is the WO of 5wt.% x/ Fe 2o 3catalyst n H 3-SCR operating temperature window is significantly widened, in middle high temperature range, have good NO xpurification efficiency, N 2generate selective and anti-SO 2poisoning performance, is applicable to stationary source and moving source NO xcatalytic removal;
(3) tungsten oxide WO xfinishing effectively improves Fe 2o 3the surface acidity of catalyst, facilitates reducing agent NH 3in the absorption of catalyst surface, effectively NO can be improved xcatalytic reduction efficiency;
(4) tungsten oxide WO xfinishing significantly have adjusted Fe 2o 3the redox ability of catalyst, inhibits reducing agent NH 3non-selective oxidation reaction, make more reducing agent NH 3can participate in SCR reaction and go, improve NO simultaneously xpurification efficiency and N 2generate selective.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 1wt.%.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1) iron nitrate solution is prepared, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 10:1,12h is stirred continuously under 90 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 100 DEG C of oven drying 5h afterwards, last in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, obtain Fe 2o 3;
(2) under oxalic acid existence condition, preparation ammonium tungstate solution, control WO xthe mass percent accounting for described catalyst is 1wt.%, in ammonium tungstate solution, add Fe 2o 3powder, stirs after 1h, through rotary evaporation at 80 DEG C by solution evaporate to dryness, 100 DEG C of dry 5h, finally in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, compressing tablet sieves into 40-60 order, obtains tungsten oxide WO xthe Fe of finishing 2o 3catalyst.
Embodiment 2
A kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 5wt.%.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1) iron nitrate solution is prepared, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 10:1,12h is stirred continuously under 90 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 100 DEG C of oven drying 5h afterwards, last in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, obtain Fe 2o 3;
(2) under oxalic acid existence condition, preparation ammonium tungstate solution, control WO xthe mass percent accounting for described catalyst is 5wt.%, in ammonium tungstate solution, add Fe 2o 3powder, stirs after 1h, through rotary evaporation at 80 DEG C by solution evaporate to dryness, 100 DEG C of dry 5h, finally in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, compressing tablet sieves into 40-60 order, obtains tungsten oxide WO xthe Fe of finishing 2o 3catalyst.
Embodiment 3
A kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 10wt.%.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1) iron nitrate solution is prepared, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 10:1,12h is stirred continuously under 90 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 100 DEG C of oven drying 5h afterwards, last in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, obtain Fe 2o 3;
(2) under oxalic acid existence condition, preparation ammonium tungstate solution, control WO xthe mass percent accounting for described catalyst is 10wt.%, in ammonium tungstate solution, add Fe 2o 3powder, stirs after 1h, through rotary evaporation at 80 DEG C by solution evaporate to dryness, 100 DEG C of dry 5h, finally in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, compressing tablet sieves into 40-60 order, obtains tungsten oxide WO xthe Fe of finishing 2o 3catalyst.
Embodiment 4
A kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 2wt.%.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1) iron nitrate solution is prepared, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 8:1,15h is stirred continuously under 80 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 90 DEG C of oven drying 8h afterwards, last in Muffle furnace, under air atmosphere in 400 DEG C of roasting 5h, obtain Fe 2o 3;
(2) under oxalic acid existence condition, preparation ammonium tungstate solution, control WO xthe mass percent accounting for described catalyst is 2wt.%, in ammonium tungstate solution, add Fe 2o 3powder, stirs after 0.5h, through rotary evaporation at 70 DEG C by solution evaporate to dryness, 90 DEG C of dry 8h, finally in Muffle furnace, under air atmosphere in 400 DEG C of roasting 5h, compressing tablet sieves into 40-60 order, obtains tungsten oxide WO xthe Fe of finishing 2o 3catalyst.
Embodiment 5
A kind of Fe of tungsten oxide finishing 2o 3catalyst, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 6wt.%.
A kind of Fe of tungsten oxide finishing 2o 3the preparation method of catalyst, described method comprises the steps:
(1) iron nitrate solution is prepared, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 12:1,8h is stirred continuously under 100 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 110 DEG C of oven drying 3h afterwards, last in Muffle furnace, under air atmosphere in 600 DEG C of roasting 2h, obtain Fe 2o 3;
(2) under oxalic acid existence condition, preparation ammonium tungstate solution, control WO xthe mass percent accounting for described catalyst is 6wt.%, in ammonium tungstate solution, add Fe 2o 3powder, stirs after 1.5h, through rotary evaporation at 90 DEG C by solution evaporate to dryness, 110 DEG C of dry 3h, finally in Muffle furnace, under air atmosphere in 600 DEG C of roasting 2h, compressing tablet sieves into 40-60 order, obtains tungsten oxide WO xthe Fe of finishing 2o 3catalyst.
Get the Fe of surperficial unmodified 2o 3material and different WO xthe WO of load capacity x/ Fe 2o 3catalyst series (embodiment 1 ~ 3), catalyst volume 0.6mL, 40-60 order, puts into catalyst activity evaluating apparatus, and activity rating carries out in fixed bed reactors.Simulated flue gas consists of (500ppm NH 3, 500ppm NO, 5%O 2), N 2for Balance Air, total flow is 500mL/min, and reaction velocity is 50000h -1.Test result is as shown in the table:
Can be obtained by upper table:
The Fe of surface unmodified 2o 3material NH 3-SCR catalytic activity is extremely low, and operating temperature window is extremely narrow, and has a large amount of N 2o accessory substance generates, and passes through WO xafter finishing, NH 3-SCR catalytic activity and N 2generate selective all have very significantly improve.Described optimal catalyst (5wt.%WO x/ Fe 2o 3) have in high temperature range in 300-450 DEG C more than 80% NO xpurification efficiency, and there is very excellent anti-SO 2poisoning performance, SO 2the poisoning front and back SCR activity of this catalyst in whole temperature section does not all have significant change.
It should be noted that and understand, when not departing from the spirit and scope of the present invention required by accompanying claim, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (48)

1. the Fe of a tungsten oxide finishing 2o 3catalyst, is characterized in that, described catalyst has following chemical composition: WO x/ Fe 2o 3, x=2 ~ 3, described WO xthe mass percent accounting for described catalyst is 1 ~ 10wt.%;
The Fe of described tungsten oxide finishing 2o 3the preparation method of catalyst, comprises the steps:
(1) prepare source of iron solution, add excess urea precipitating reagent in solution, make precipitation of iron ions complete, by the precipitated product suction filtration obtained, washing, dry, roasting, obtains Fe 2o 3;
(2) under oxalic acid existence condition, preparation tungsten source solution, adds Fe in the solution of tungsten source 2o 3powder, after stirring through rotary evaporation by solution evaporate to dryness, dry, roasting, obtains the Fe of tungsten oxide finishing 2o 3catalyst.
2. catalyst as claimed in claim 1, is characterized in that, described WO xthe mass percent accounting for described catalyst is 1.5 ~ 8.5wt.%.
3. catalyst as claimed in claim 2, is characterized in that, described WO xthe mass percent accounting for described catalyst is 3 ~ 6wt.%.
4. catalyst as claimed in claim 3, is characterized in that, described WO xthe mass percent accounting for described catalyst is 5wt.%.
5. the Fe of the tungsten oxide finishing as described in one of claim 1-4 2o 3the preparation method of catalyst, is characterized in that, described method comprises the steps:
(1) prepare source of iron solution, add excess urea precipitating reagent in solution, make precipitation of iron ions complete, by the precipitated product suction filtration obtained, washing, dry, roasting, obtains Fe 2o 3;
(2) under oxalic acid existence condition, preparation tungsten source solution, adds Fe in the solution of tungsten source 2o 3powder, after stirring through rotary evaporation by solution evaporate to dryness, dry, roasting, obtains the Fe of tungsten oxide finishing 2o 3catalyst.
6. method as claimed in claim 5, is characterized in that, described source of iron is selected from the mixture of any one or at least two kinds in ferric nitrate, ferric sulfate, ferric phosphate or iron chloride.
7. method as claimed in claim 6, it is characterized in that, described source of iron is ferric nitrate.
8. method as claimed in claim 5, it is characterized in that, urea/source of iron mol ratio is 8 ~ 12:1.
9. method as claimed in claim 8, it is characterized in that, urea/source of iron mol ratio is 10:1.
10. method as claimed in claim 5, it is characterized in that, described precipitation temperature is 80 ~ 100 DEG C.
11. methods as claimed in claim 10, it is characterized in that, described precipitation temperature is 90 DEG C.
12. methods as claimed in claim 5, is characterized in that, the time of described precipitation is 8 ~ 15h.
13. methods as claimed in claim 12, is characterized in that, the time of described precipitation is 9 ~ 13h.
14. methods as claimed in claim 13, is characterized in that, the time of described precipitation is 12h.
15. methods as claimed in claim 5, is characterized in that, the temperature of step (1) described drying is 90 ~ 110 DEG C.
16. methods as claimed in claim 15, is characterized in that, the temperature of step (1) described drying is 95 ~ 105 DEG C.
17. methods as claimed in claim 16, is characterized in that, the temperature of step (1) described drying is 100 DEG C.
18. methods as claimed in claim 5, is characterized in that, the time of step (1) described drying is 3 ~ 8h.
19. methods as claimed in claim 18, is characterized in that, the time of step (1) described drying is 3.5 ~ 6.5h.
20. methods as claimed in claim 19, is characterized in that, the time of step (1) described drying is 5h.
21. methods as claimed in claim 5, it is characterized in that, step (1) described roasting is carried out in air atmosphere, and described sintering temperature is 400 ~ 600 DEG C.
22. methods as claimed in claim 21, it is characterized in that, step (1) described roasting is carried out in air atmosphere, and described sintering temperature is 500 ~ 600 DEG C.
23. methods as claimed in claim 22, it is characterized in that, step (1) described roasting is carried out in air atmosphere, and described sintering temperature is 500 DEG C.
24. methods as claimed in claim 5, it is characterized in that, step (1) described roasting time is 2 ~ 5h.
25. methods as claimed in claim 24, it is characterized in that, step (1) described roasting time is 3h.
26. methods as claimed in claim 5, it is characterized in that, described tungsten source is selected from tungstates or/and tungsten phosphate.
27. methods as claimed in claim 26, it is characterized in that, described tungsten source is selected from ammonium tungstate or/and sodium tungstate.
28. methods as claimed in claim 27, it is characterized in that, described tungsten source is selected from ammonium tungstate.
29. methods as claimed in claim 5, is characterized in that, the time of step (2) described stirring is 0.5 ~ 1.5 hour.
30. methods as claimed in claim 29, is characterized in that, the time of step (2) described stirring is 1 hour.
31. methods as claimed in claim 5, is characterized in that, the temperature of described rotary evaporation evaporate to dryness is 70 ~ 90 DEG C.
32. methods as claimed in claim 31, is characterized in that, the temperature of described rotary evaporation evaporate to dryness is 73 ~ 87 DEG C.
33. methods as claimed in claim 32, is characterized in that, the temperature of described rotary evaporation evaporate to dryness is 80 DEG C.
34. methods as claimed in claim 5, is characterized in that, the temperature of step (2) described drying is 90 ~ 110 DEG C.
35. methods as claimed in claim 32, is characterized in that, the temperature of step (2) described drying is 95 ~ 105 DEG C.
36. methods as claimed in claim 35, is characterized in that, the temperature of step (2) described drying is 100 DEG C.
37. methods as claimed in claim 5, is characterized in that, the time of step (2) described drying is 3 ~ 8h.
38. methods as claimed in claim 37, is characterized in that, the time of step (2) described drying is 3.5 ~ 6.5h.
39. methods as claimed in claim 38, is characterized in that, the time of step (2) described drying is 5h.
40. methods as claimed in claim 5, it is characterized in that, step (2) described roasting is carried out in air atmosphere, and described sintering temperature is 400 ~ 600 DEG C.
41. methods as claimed in claim 40, it is characterized in that, step (2) described roasting is carried out in air atmosphere, and described sintering temperature is 500 ~ 600 DEG C.
42. methods as claimed in claim 41, it is characterized in that, step (2) described roasting is carried out in air atmosphere, and described sintering temperature is 500 DEG C.
43. methods as claimed in claim 5, it is characterized in that, step (2) described roasting time is 2 ~ 5h.
44. methods as claimed in claim 5, it is characterized in that, step (2) described roasting time is 3h.
45. methods as claimed in claim 5, is characterized in that, sieve step (2) product of roasting compressing tablet 20 ~ 80 orders.
46. methods as claimed in claim 45, is characterized in that, sieve step (2) product of roasting compressing tablet 40 ~ 60 orders.
47. methods as claimed in claim 5, it is characterized in that, described method comprises the steps:
(1 ') preparation iron nitrate solution, excess urea precipitating reagent is added in solution, urea/source of iron mol ratio is 10:1,12h is stirred continuously under 90 DEG C of water bath condition, make precipitation of iron ions complete, suction filtration and washing are carried out to sediment, filter cake is put in 100 DEG C of oven drying 5h afterwards, last in Muffle furnace, under air atmosphere in 500 DEG C of roasting 3h, obtain Fe 2o 3;
(2 '), preparation ammonium tungstate solution, added Fe in ammonium tungstate solution under oxalic acid existence condition 2o 3powder, stirs after 1h, through rotary evaporation at 80 DEG C by solution evaporate to dryness, 100 DEG C of dry 5h, finally in air atmosphere in 500 DEG C of roasting 3h, compressing tablet sieves into 40-60 order, obtains the Fe of tungsten oxide finishing 2o 3catalyst.
The Fe of 48. 1 kinds of tungsten oxide finishinges as described in one of claim 1-4 2o 3the purposes of catalyst, is characterized in that, described catalyst is used for NH 3selective Catalytic Reduction of NO x.
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CN109331835A (en) * 2018-12-05 2019-02-15 黑龙江大学 A kind of ammonia-selective catalyst reduction of nitrogen oxides catalyst and its preparation method and application
CN110586118A (en) * 2019-10-11 2019-12-20 上海理工大学 Magnetic iron-based catalyst for selective catalytic reduction denitration and preparation method thereof
CN112593248B (en) * 2020-12-15 2021-09-03 苏州大学张家港工业技术研究院 Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof

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